Process for producing oil-soluble metal sulfonates

ABSTRACT

A process for producing oil-soluble metal sulfonates is disclosed wherein a metal halide is reacted with an oil-soluble sulfonic acid to produce the desired metal sulfonate. The metal constituent of the metal halide is selected from the group consisting of aluminum, indium, chromium, iron, molybdenum, vanadium, titanium, niobium, tantalum, rubidium, and osmium.

United States Patent 1191 Sias ,1 1 July 29, 1975 [5 1 PROCESS FORPRODUCING ,OlL-SOLUBLE 2,430,815 11/1947 Hersberger 260/448 R 2,779,784l/l957 Sharrah......... 260/505 N 2.865.957 12/1958 Logan 260/439 RInventor: y 0 S a o a ty. 1: 2,868,823 1/1959 Kloge =1 al.... 260/448 a[73] Assign: Communal on Company Poh-ca 3,021,280 2/1962 Carlyle....-252/33 City, Okla. FOREIGN PATENTS OR APPLICATIONS 22 Filed: M u 973l,5l L033 l2/l967 France 260/505 N 1,126.38! 3/1962 Germany 260/505 N211 Appl. 140.; 359,302

Related U.S. Application Data [63] Continuation of Ser. No. 148,264, May5, 1971,

abandoned.

[52] U.S. Cl 260/429 K; 252/33; 260/429 R; 260/4295; 260/4385 R; 260/439R; 260/448 R; 260/505 N; 260/513 R 151] Int. Cl. C07l 11/00; C071" l/OO;C07f 7/28 [58] Field of Search 260/513 R, 429 R, 429 K, 260/439 R, 448R, 505 N, 438.5, 429.5;

OTHER PUBLICATIONS Noller, Chemistry of Organic Compounds, 3rd ed.,1965, p. 505.

Primary Examiner-Arthur P. Demers Attorney, Agent, or Firm-Robert B.Coleman, Jr.

[57] ABSTRACT A process for producing oil-soluble metal sulfonates isdisclosed wherein ametal halide is reacted with an oilsoluble sulfonicacid to produce the desired metal sulfonate. The metal constituent ofthe metal halide is selected from the group/consisting of aluminum,indium, chromium, iron, molybdenum, vanadium, titanium, niobium,tantalumpmbidium, and osmium.

l2 Ga'ims, No Drawings PROCESS FOR PRODUCING OIL-SOLUBLE METALSULFONATES This is a continuation of application Ser. No. 148.264. filedMay 5. 1971 and now abandoned.

BACKGROUND OF THE INVENTION from oil-soluble metal sulfonates and metaldispersions in such sulfonates by dissolving such materials inpredetermined quantities in a suitable solvent. Such stan- El'tirtlshave exhibited indefinite shelf life and any combinatia'fi of metals canbe combined without precipitation of the metal constituents.

Further. dispersions containing certain oil-soluble metal sulfonateshave acquired considerable importance additives in fuels and lubricatingoil. Such dispersions have been highly useful as additives to othermaterials where the problem of suspending insoluble waste materialsformed in the utilization of the material and also the problem ofcorrosion inhibition is met. When the oil-soluble metal sulfonates areemployed as additives for use in internal combustion engine lubrieatingcompositions. such agents function to effectively disperse or peptizethe insolubles formed by the fuel combustion. oil oxidation. or similarconditions obtained during the operation of the engine.

Thus. while the use of oil-soluble metal sulfonates have beenestablished and recognized. problems have beet! encountered in theproduction of oil-soluble metal sulfonates of certain metals. such asmolybdenum. aluminum and iron. Therefore, a need has long beenrecognized for an improved process for the production of oilsolublemetal sulfonates from readily available chemical compounds. and it is tosuch a pro eess that the present invention is directed.

OBJECTS OF THE INVENTION These and other objects. advantages. andfeatures of the present invention would be apparent to those skilled inthe art from a reading of the following detailed description.

SUMMARY OF THE INVENTION According to the present invention I have founda process for producing oil-soluble metal sulfonates wherein the metalconstituent is selected from aluminum. chromium. iron. molybdenum.vanadium. titanium. indium. niobium. tantalum. rubidium. and osmiumwhich comprises admixing a halide compound of such metals with anoil-soluble sulfonic acid. heating the resulting mixture to its refluxtemperature for a period of time effective to allow formation of theoilsoluble metal sulfonate.

Further according to the invention l have found that it is desirable forsaid metal halide to be present in a stoichiometric excess of from 5 toabout 200% with said oil-soluble sulfonic acid. A volatile inert solventcan be incorporated with the oil-soluble sulfonic acid to reduce theviscosity of same and to facilitate the admixing of the oil-solublesulfonate with said metal halide.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Oil-soluble metal sulfonateshave been recognized as desirable analytical standards as well asoil-soluble additives for fuels and lubricants. However. problems havebeen encountered in producing oil-soluble metal sulfonates such asmolybdenum sulfonate. iron sulfonate and aluminum sulfonate.

l have now found that oil-soluble metal sulfonates of aluminum.chromium. iron. molybdenum. vanadium. titanium. indium. niobium.tantalum. rubidium. and osmium can readily be prepared by reacting ahalide compound. or a mixture of a halide compound and oxide compound.of such metal with an oil-soluble sulfonic acid at elevated temperaturesfor a period of time effective to allow said halide compound or amixture of a metal halide and a metal oxide compound to react with saidoil-soluble sulfonic acid to produce the desired oil-soluble metalsulfonate.

The present invention can be carried out as either a batch process or acontinuous process. However. for the sake of simplicity the process ofthe present invention will be described as a batch process.

The metal halide and the oil-soluble sulfonic acid are charged to areaction vessel equipped with heating means. a stirring means and areflux means. Generally. it is desirable to introduce an effectiveamount of an inert volatile solvent to the reaction mixture to reducethe viscosity of the oil-soluble sulfonic acid thereby facilitating themixing and contact between the reactants. The amount ofinert volatilesolvent employed can vary widely depending upon the viscosity of theparticular oil-soluble sulfonic acid employed well as the viscositydesired in the reaction mixture but will generally be in an amountranging from about 25 to I50 weight percent. based on the weight of thereaction mixture. The amount of the reactants can vary widely. However.the metal halide should be present in a stoichiometric excess.Generally. the excess will range from about 5 to 200 percent with themost desirable amount ranging from 5 to about 15 percent.

Once the reactants have been introduced into the reaction vessel thereactants are thoroughly agitated and the reaction mixture is heated toits reflux temperature which will generally be within the range of about60 to l05 (I. When desirable an additional amount of the oil-solublesulfonic acid can be introduced into the reaction mixture during theheating period before the mixture reaches its reflux temperature.However. care must be exercised to insure that the introduction of theadditional oil-soluble sulfonic acid does not dilute the reactionmixture to such an extent that the metal halide is no longer present ina stoichiometric excess. Generally. when additional oil-soluble sulfonicacid is introduced the amount will range from about 50 to 100 weightpercent based on sulfonic acid present and at a temperature in the rangeof about 60 to 105 C.

When the reaction mixture reaches its reflux temperature it ismaintained at such temperature under reflux conditions for an effectiveperiod of time to allow the metalhalide and oil-soluble sulfonic acid toreact and form the desired oil-soluble meal sulfonate. The reflux timeof the reaction mixture can vary widely but will generally range fromabout I to about 6 hours. It is often desirable to introduce to themixture after same has refluxed for about 1 to 6 hours from about I toweight percent water based on sulfonic acid. The reaction mixturecontaining the water is then maintained at reflux conditions for anadditional period of time ranging from 0.l to 2 hours.

After the above-described reflux steps have been carried out the mixtureis stripped of the volatile components. Any suitable method for removingthe volatile components can be employed such as heating the mixture to atemperature from about 125 to 175C. From about 20 to 300 weight percentofa nonvolatile organic carrier component (based on sulfonic acid] isintroduced at any convenient point. such as during the reflux period.Residual volatile material is removed by any suitable means such asvacuum stripping or stripping said mixture with a gas such as nitrogen.carbon dioxide. air and the like for a period of time ranging from 0.2to 6 hours. The stripped product normally is clarified by filtration ofthe stripped product through a desirable inert absorbent such asalumina. diatomaceous earth, pumice and the like.

The metal halide which can be employed in the production of theoil-soluble metal sulfonates can be any suitable halide ofaluminum.chromium. iron. molybdenum. vanadium. titanium. indium. niobium.tantalum, rubidium. and osmium. Examples of such halides are aluminumchloride. aluminum bromide. aluminum fluoride. chromium chloride.chromium bromide, chromium fluoride. ferric chloride. ferric bromide,ferric fluoride. molybdenum fluoride. vanadium chloride, vanadiumbromide. vanadium fluoride. titanium chloride. titanium bromide.titanium fluoride. indium chloride. indium bromide. indium fluoride.niobium chloride. niobium bromide. niobium fluoride. tantalum chloride.tantalum bromide. tantalum fluoride. rubidium chloride. rubidiumbromide. rubidium fluoride. osmium chloride. osmium bromide. and osmiumfluoride. Especially desirable results have been obtained wherein themetal halide is the metal chloride. In addition. mixtures of the metalhalide and a metal oxide can be employed. When such a mixture isemployed the metal halide will be present in such mixture in an amountranging from about 0.25 to 8 moles per mole metal oxide. Examples ofsuitable mixtures of the halide and oxide components are: AlCl;,'Al-,O;. (and hydrates); FeCl -Fe O CrClybH OCr o TiCl.-'li()- and the like.

Suitable oil-soluble hydrocarbon sulfonic acids include alkane sulfonicacid. aromatic sulfonic acid. alkaryl sulfonic acid. aralkyl sulfonicacid. and the natural petroleum mahogany sulfonic acids. The mahoganysulfonic acids include any of those materials which may be obtained byconcentrated or fuming sulfuric acid treatment of petroleum fractions.particularly the higher boiling lubricating oil distillates and whiteoil distillates. The higher molecular weight petroleum oilsolublemahogany sulfonic acids are condensedring compounds. whichcondensed-rings may be aromatic or hydroaromatic in nature. Alkyl and/orcycloalkyl substituents may be present in the mahogany sulfonic acids.

The terms oil-soluble sulfonic acids." as used herein. refers to thosematerials wherein the hydrocarbon portion of the molecule has amolecular weight in the range of about 300 to about 1.000. Preferably.this molecular weight is in the range of about 370 to about 700. Theseoilsoluble sulfonic acids can be either synthetic sulfonic acids or theso-called mahogany or natural sulfonic acids. The term mahogany sulfonicacid is believed to be well understood. since it is amply described inthe literature. The term synthetic sulfonic acids" refers to thosematerials which are prepared by sulfonation of hydrocarbon feedstockswhich are pre pared synthetically. The synthetic sulfonic acids can bederived from either alkyl or alkaryl hydrocarbons. in addition. they canbe derived from hydrocarbons having cycloalkyl (i.e.. naphthenic) groupsin the side chains attached to the benzene ring. The alkyl groups in thealkaryl hydrocarbons can be straight or branched chain. The alkarylradical can be derived from benzene. toluene. ethyl benzene. xyleneisomers. or naphthalene.

An example of a hydrocarbon feedstock which has been particularly usefulin preparing synthetic sulfonic acids is a material known aspostdodecylbenzene. Postdodecylbenzene is a bottoms product of themanufac ture of dodecylbenzene. The alkyl groups of postdodecylbenzeneare branched chain. Postdodecylbenzene consists of monoalkylbenzenes anddialkylbenzenes in the approximate mole ratio of 2:3 and has typicalproperties as follows:

Specific gravity at 38 degrees C 0.8649 Average molecular weight 385Percent sulfonatable 88 ASTM D-lSR Engler:

l.B.P.. degrees F 647 5 degrees F 682 50 degrees F 715 90 degrees F 760degrees F 775 F.B.P. degrees F 779 Refractive index at 23 degrees C 11.4900 Viscosity at:

l0 degrees C. ccntistokes 2800 20 degrees C. ccntistokes 280 40 degreesC. centistokes 78 80 degrees C. centistokes l8 Aniline point. degrees C6) Pour Point. degrees F 25 An example of another hydrocarbon feedstockwhich is particuarly useful in preparing synthetic sulfonic acids is amaterial referred to as dimer alkylate. "Dimer alkyl-ate" has a longbranched-chain alkyl group. Briefly described. dimer alkylate isprepared by the following steps:

1. dimerization of a suitable feedstock. such as cat poly gasoline; and

2. alkylation of an aromatic hydrocarbon with the dimer formed in step tl Preferably, the dimerization step uses a FriedeLC'rafts alkylationsludge as the catalyst. This process and the resulting product aredescribed in US. Pat. 3.410.925.

An example of another hydrocarbon feedstock which is particularly usefulfor preparing synthetic sulfonic acids which can be used in my inventionis a material which I refer to as NAB Bottoms." NAB Bottoms arepredominantly di-n-alkyl aromatic hydrocarbon wherein the alkyl groupscontain from eight to l8 carbon atoms. They are distinguished primarilyfrom the preceding sulfonation feedstocks in that they are straightchain and contain a large amount of disubstituted material. A process ofpreparing these materials and the resulting product are described inapplication Ser. No. 62.211. filed Aug. 7. l970. and being acontinuation-in-part of application Ser. No. 529.284. filed Feb. 23.1966. and now abandoned. Application Ser. Nos. 62.21 I and 529.284 havethe same assignee as the present application. The product is alsodescribed in US. Pat. No. 3.288.716, which is concerned with anadditional use for the product. other than sulfonation feedstock.Another process of preparing these materi als is described inapplication Ser. No. 53.352, filed Aug. 6, 1970. and having the sameassignee as the present application. Application Ser. No. 53.352 is acontinuationJn-part of application Ser. No. 529.284. Still anotherprocess of preparing a di nalkaryl product is described in applicationSer. No. [04.476. filed Jan. 7. I97]. which is a continuation-in-part ofapplication Ser. No. 52l.794. filed Jan. 20. 1966. and now abandoned.

In order to make my disclosure even more complete. U.S. Pat. No.3.410.925 and application Ser. Nos. 53.352; 62.2ll and 104.7476, aremade a part of this disclosure.

In addition to the sulfonic acids derived from the foregoing describedhydrocarbon feedstock. examples of other suitable sulfonic acids includethe following: mono and poly-substituted naphthalene sulfonic acid.dinonyl naphthalene sulfonic acid. diphertyl ether sulfonic acid.naphthalene disulfide sulfonic acid, dicetyl thianthrene sulfonic acid.dialauryl betanaphthol sulfonic acid. dicapryl nitronaphthalene sulfonicacid. unsaturated paraffin wax sulfonic acid. hydroxy substitutedparaffin wax sulfonic acid. tetraamylene sulfonic acid. monoandpoly-chlorosubstituted paraffin wax sulfonic acid. nitrosoparaffin waxsulfonic acid, cycloaliphatic sulfonic acid such as lauryl-cyclohexylsulfonic acid. monoand polywax-substituted cyclohexyl sulfonic acid. andthe like.

The corresponding hydrocarbon sulfonic acid is usu' ally prepared bytreating the hydrocarbon with concentrated sulfuric acid. fuming sulfuracid or sulfur trioxide. The sulfonation of hydrocarbons is well knownand details need not be given. The sulfonic acid may also be purified byany suitable means: i.e.. treatment with inorganic base. ion exchange,water washing and the like.

As previously stated the oil-soluble sulfonic acid is often diluted witha volatile solvent. The volatile solvent can be any suitablehydrocarbon. preferably a low boiling hydrocarbon such as hexane ornaphtha which may readily be removed from the metal sulfonatc prod uctwhen desired.

With respect to the types of nonvolatile carriers which may be utilizedin the process. a wide variety of materials have been found suitable forsuch usage. The principal requisites desired in the nonvolatile carrierare that it will dissolve the dispersing agents utilized in the process.and that such solutions will be relatively stable when the basicmetallic compounds are peptized in the dispersion by the dispersingagent. Examples of such nonvolatile carriers which may be employedinclude mineral lubricating oil obtained by any of the conventionalrefining procedures; vegetable oils. such as corn oil. cottonseed oil.castor oil. etc: animal oil. such as lard oil. sperm oil. etc; andsynthetic oils. such as polymers of propylene. polyoxyalkylenes.polyoxypropylene, dicarbosylic acid esters. such as esters of adipic andazelaic acids with alcohols such as butyl. 2- ethyl hexyl and dodecylalcohols. and esters of acids of phosphorus. such as diethyl ester ofdecanephosphonic acid and tricresyl phosphate. The preferred nonvolatilecarriers are liquid lubricating oils. either mineral or synthetic. Inaddition, sulfonic acid stock such as previously described hereinahovecan be employed as the nonvolatile carrier. If desired. the nonvolatilecarriers may be diluted with a solvent to reduce the viscosity. Suitablesolvents include petroleum naphtha or hydrocarbons. such as hexane.heptanc. octane. benzene. toluene. or xylene.

In order to more fully illustrate the nature of the present inventionthe following examples are given. However. it is to be understood thatthe examples are for illustrative purposes only and are not intended tounduly limit or restrict the scope of the present invention. In eachexample the sulfonic acid was derived frm an alkylaromatic which waspredominantly di-nalkylbenzenes having a combined molecular weight ofabout 420. unless otherwise specified.

EXAMPLE I To a creased l-liter flask was charged 2 l 2.0 grams ofsulfonic acid and 27.4 grams of anhydrous MoCl; during mechanicalagitation. Heat was applied and the reaction was taken to 70 C.whereupon an additional 2 l 2.0 grams of sulfonic acid was charged andthe reaction taken to reflux temperature and refluxed for 2 hours. 5 ml.water was charged followed by additional refluxing. then the volatileswere taken overhead to a pot temperature of 150 C; 170 grams'of 80 paleoil was charged at about l 10 C. The product was then stripped with Ngas for 15 minutes and filtered through Hyflo. The product was analyzedand found to contain 2.6 weight percent molybdenum and 0.04 weightpercent chlorine.

EXAMPLE 2 Sulfonic Acid 2 l 2.0 grams l2.8 t grams Anhydrous Mocls, 80.I. grams 80 Palc Oil ll) ml. Water The product produced was filtered asin Example l and found to contain l.7 weight percent molybdenum.

EXAMPLE 3 The general procedure described in Example 2 was, followed.The charge employed was as follows:

250 grams Sulfonic Acid 34.) grams CrClflsHJ) I20 grams 8i) Pale Oil Themixture of the acid and chromium compound was heated to its refluxtemperature and maintained under reflux conditions for 2 hours. The paleoil was then added to the mixture at 100 C. After additional refluxingthe product was heated to l(l C and stripped for l5 minutes with N gas.The stripped product was then filtered and analyzed to contain 2.4weight percent chromium and 0.02 weight percent chlorine.

i g EXAMPLE 4 The procedureof Examplel is employed in this example. Thesulfonic acid was charged in two equal increments of 125 grams. Thetotal charge to the reaction flask is as follows:

I 25H grams Sullonic Acid l6.-l grams Anhydrous (rCl 12H grams 8U PaleOil EXAMPLE 5 An experiment was conducted on the production of ironsulfonatissusing the general procedure of Example 2 wherein all thesulfonic acid was charged at ambient temperature. The charge employedwas as follows:

135 grams Stillonic Acid 3H1) grams Ht) Pale Oil Uh grams Anhydrous FcClliLU grams Water The sulfonic acid-FeCL, mixture was heated to itsreflux temperature and refluxed for 2 hours. Ten milliliters of waterwas then charged followed by additional refluxing. The volatiles werethen taken overhead to a pot temperature of l50 C. The pale oil was thencharged to the mixture at about I it) C. The resulting product was thenstripped with N gas for about 15 minutes and filtered. The product wasanalyzed and found to contain 2.4 weight percent iron.

EXAMPLE (1 To a creased one-liter flask was charged l 13.3 grams ofsulfonic acid and 21.8 grams of FeCl oH O during mechanical agitation.The sulfonic acid was diluted r with 50 milliliters of n'heptane. Heatwas applied and the reaction mixture was taken to C whereupon anadditional i 13.0 grams of sulfonic acid was charged to the mixture.Theresulting reaction mixture was then heated to a pot temperature ofabout C at which point about 13o milliliters of volatile materials wereremoved overhead. The mixture was then refluxed for 2 hours. At the endof the reflux period the volatile components remaining were takenoverhead to a pot temperature of l50 C. The product remaining was thenstripped with N gas at C for 45 minutes. The pale oil was then chargedto the stripped product. The resulting product was filtered and found tocontain 2.5 weight percent iron and less than 0.0l weight percentchlorine.

EXAMPLE 7 in this experiment the sulfonic acid was charged to a reactionflask and residual water was removed by azeotropic distillation. Thesulfonic acid was then employed to prepare a niobium sulfonatecomposition as follows:

The charge employed was:

209 grams Sulfonic Acid 12 grams Anhydrous NbCl l8 grams 8U Pale Oil Thegeneral procedure of Example l was followed. The sulfonic acid wascharged in equal increments and the reflux period was 2 hours. The 80pale oil was charged to the mixture at l25 C and the product wasstripped with N gas for 15 minutes at l50 C. The product was filteredand found to contain 3.3 weight percent niobium and less than 0.01weight percent chlorine.

The above examples clearly indicate the preparation of oil-soluble metalsulfonates by the process of the present invention.

Having thus described the invention, I claim:

1. A process for producing oil-soluble sulfonates containing metalconstituents, which sulfonates have a long shelf life withoutprecipitation of the metal constituents, comprising:

a. mixing at least a stoichiometric amount of a metal halide selectedfrom the group consisting of aluminum. chromium. iron, molybdenum.vanadium. titanium, indium, niobium, tantalum. rubidium, osmium. andmixtures thereof, with water and an oilsoluble sulfonic acid having amolecular weight in the range of about 300 to about 1000 to form areaction mixture.

b. agitating and heating said reaction mixture to a temperature in therange of 60 to [05C.

c. introducing into the reaction mixture an additional amount of theoil-soluble sulfonic acid in an amount of from 50 to 200 weight percentbased on the oil-soluble sulfonic acid already in the reaction mixture.

d. continuing the agitation and heating of the reaction mixture to thereflux temperature of said mixture for a period of time effective toallow formation of a metal sulfonate substantially free of said halide.and

e. recovering from the reaction product of step (d) the metal sulfonate.

2. The process of claim l wherein said oil-soluble sulfonic acid isdiluted with from about 15 to lSU weight percent of an inert volatilesohcnt and said reflux temperature is in the range of about 60 to l05 C.

3. The process of claim 2 wherein said inert volatile solvent is a lowboiling hydrocarbon selected from the group consisting of hexane andnaphtha.

4. The process of claim 1 wherein said reaction mixture is maintained atits reflux temperature for a period of time ranging from about 1 to 6hours.

5. The processs of claim 4 which includes the step of admixing fromabout l to about weight percent water. based on the amount ofsulfonicacid employed. to said mixture after same has refluxed and then heatingthe mixture to its reflux temperature and maintaining same under refluxcondition for a period of time ranging from 0.1 to 2 hours.

6. The process of claim 1 wherein the refluxed mixture is stripped ofvolatile components by heating said refluxed mixture to a temperaturewithin the range of about l25 to 175C and includes the step of admixingfrom about 20 to 300 weight percent of a nonvolatile organic carriercomponent to said reflux mixture during refluxing of same.

7. The process of claim 6 which includes the additional purificationsteps of stripping the product with an inert gas selected from the groupconsisting of nitrogen. carbon dioxide. air. and mixtures thereof for aperiod of time ranging from about 0.2 to 6 hours and liltering the gasstripped product through an inert absor- Beat hiatetlal selected fromthe group consisting of alurains, diatoma'c'eous earth and pumice.

8. The process of claim 7 wherein said metal halide is present in amixture of said metal halide and a metal oxide. said metal halide beingpresent in said mixture in an amount ranging from about 0.25 to 8 molesof said metal halide per mole of said metal oxide.

9. The process of claim 8 wherein said oil-soluble sulfonic acid has amolecular weight in the range of about 370 to about 700 and is producedsynthetically by the sulfonation of an alkylate selected from the groupconsisting of dimer alkylate and NAB Bottoms alkylate. and saidnonvolatile carrier component is pale oil.

10. The process of claim 9 wherein said nonvolatile carrier is dilutedwith a solvent selected from the group consisting of petroleum naphtha.hexane, heptane. octane. benzene. toluene. and xylene.

ll. A process for producing oil-soluble sulfonates containing metalconstituents. which sultonates have a long shelf life withoutprecipitation of the metal constituents. comprising:

a. mixing at least a stoichiometric amount of a metal halide selectedfrom the group consisting otaluminum. chromium. iron. molybdenum.vanadium. titanium. indium. niobium. tantalum. rubidium. osmium. andmixtures thereof. with water and an oilsoluble sulfonic acid having amolecular weight in the range of about 300 to about L000 to form areaction mixture.

b. agitating and heating said reaction mixture to the reflux temperatureof said mixture for a period of time effective to allow formation of ametal sulfonate substantially free of said halide. and admixing fromabout 1 to about 25 weight percent water. based on the amount ofsulfonic acid employed. to said mixture after same has refluxed and thenheating the mixture to its reflux temperature and maintaining same underreflux condition for a period of time ranging from 0.1 to 2 hours.

d. recovering from the reaction product of step (c) the metal sulfonate.

12. The process of claim ll which includes the step of admixing fromabout 50 to 200 weight percent additional oil-soluble sulfonic acid tosaid reaction mixture during the heating of said mixture. and while saidmixture is at a temperature within the range of about 60 to 105C.

l i l UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. L3, 97,470

DATED July 29, 1975 |NVENTOR(S) Roy C. Sias tt is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below Column 3, line 18, change '"meal"to"metal" Signed and Scaled this seventeenth D ay Of February I 9 76[SEAL] A rresr:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (mnmr'xsr'mreruj'Parenrs and Trademarks

1. A PROCESS FOR PRODUCING OIL-SOLUBLE SULFONATES CONTAINING METALCONSTITUENTS, WHICH SULFONATES HAVE A LONG SHELF LIKE WITHOUTPRECIPITATION OF THE METAL CONSTITUENTS, COMPRISING: A. MIXING AT LEASTA STOICHIOMETRIC AMOUNT OF A METAL HALIDE SELECTED FROM THE GROUPCONSISTING OF ALUMINUM, CHROMINUM, RION, MOLYBDENUM, VANADIUM, TITANIUM,INDIUM, NIOBIUM, TANTALUM, RUBIDIUM, OSMIUM, AND MIXTURES THEREOF, WITHWATER AND AN OIL-SOLUBLE SULFONIC ACID HAVING A MOLECULAR WEIGHT IN THERANGE OF ABOUT 300 TO ABOUT 1000 TO FOM A REACTION MITURE, B. AGITATINGAND HEATING SAID REACTION MIXTURE TO A TEMPERATURE IN THE RANGE OF 60*TO 105*C, C. INTRODUCING INTO THE REACTION MIXTURE AN ADDITIONAL AMOUNTOF THE OIL-SOLUBLE SULFONIC ACID IN AN AMOUNT OF FROM 50 TO 200 WEIGHTPERCENT BASED ON THE OIL-SOLUBLE SUFLONIC ACID ALREADY IN THE REACTIONMIXTURE, D. CONTINUING THE AGITATION AND HEATING OF THE REACTION MIXTURETO THE REFLUX TEMPERATURE OF SAID MIXTURE FOR A PERIOD OF TIME EFFECTIVETO ALLOW FORMATION OF A METAL SULFONATE SUBSTANTIALLY FREE OF SAIDHALIDE, AND E. RECOVERING FROM THE REACTION PRODUCT OF STEP (D) THEMETAL SULFONATE.
 2. The process of claim 1 wherein said oil-solublesulfonic acid is diluted with from about 25 to 150 weight percent of aninert volatile solvent and said reflux temperature is in the range ofabout 60* to 105* C.
 3. The process of claim 2 wherein said inertvolatile solvent is a low boiling hydrocarbon selected from the groupconSisting of hexane and naphtha.
 4. The process of claim 1 wherein saidreaction mixture is maintained at its reflux temperature for a period oftime ranging from about 1 to 6 hours.
 5. The processs of claim 4 whichincludes the step of admixing from about 1 to about 25 weight percentwater, based on the amount of sulfonic acid employed, to said mixtureafter same has refluxed and then heating the mixture to its refluxtemperature and maintaining same under reflux condition for a period oftime ranging from 0.1 to 2 hours.
 6. The process of claim 1 wherein therefluxed mixture is stripped of volatile components by heating saidrefluxed mixture to a temperature within the range of about 125* to175*C and includes the step of admixing from about 20 to 300 weightpercent of a nonvolatile organic carrier component to said refluxmixture during refluxing of same.
 7. The process of claim 6 whichincludes the additional purification steps of stripping the product withan inert gas selected from the group consisting of nitrogen, carbondioxide, air, and mixtures thereof for a period of time ranging fromabout 0.2 to 6 hours and filtering the gas stripped product through aninert absorbent material selected from the group consisting of alumina,diatomaceous earth and pumice.
 8. The process of claim 7 wherein saidmetal halide is present in a mixture of said metal halide and a metaloxide, said metal halide being present in said mixture in an amountranging from about 0.25 to 8 moles of said metal halide per mole of saidmetal oxide.
 9. The process of claim 8 wherein said oil-soluble sulfonicacid has a molecular weight in the range of about 370 to about 700 andis produced synthetically by the sulfonation of an alkylate selectedfrom the group consisting of dimer alkylate and NAB Bottoms alkylate,and said nonvolatile carrier component is pale oil.
 10. The process ofclaim 9 wherein said nonvolatile carrier is diluted with a solventselected from the group consisting of petroleum naphtha, hexane,heptane, octane, benzene, toluene, and xylene.
 11. A process forproducing oil-soluble sulfonates containing metal constituents, whichsulfonates have a long shelf life without precipitation of the metalconstituents, comprising: a. mixing at least a stoichiometric amount ofa metal halide selected from the group consisting of aluminum, chromium,iron, molybdenum, vanadium, titanium, indium, niobium, tantalum,rubidium, osmium, and mixtures thereof, with water and an oil-solublesulfonic acid having a molecular weight in the range of about 300 toabout 1,000 to form a reaction mixture, b. agitating and heating saidreaction mixture to the reflux temperature of said mixture for a periodof time effective to allow formation of a metal sulfonate substantiallyfree of said halide; and c. admixing from about 1 to about 25 weightpercent water, based on the amount of sulfonic acid employed, to saidmixture after same has refluxed and then heating the mixture to itsreflux temperature and maintaining same under reflux condition for aperiod of time ranging from 0.1 to 2 hours, d. recovering from thereaction product of step (c) the metal sulfonate.
 12. The process ofclaim 11 which includes the step of admixing from about 50 to 200 weightpercent additional oil-soluble sulfonic acid to said reaction mixtureduring the heating of said mixture, and while said mixture is at atemperature within the range of about 60* to 105*C.